Asphalt compositions



United States Patent 3,347,690 ASPHALT CGMPOSITIQNS Thomas J. Galvin andFrancis A. Hughes, Wilmington,

Del, assignors to Atlas Chemical Industries, Inc, Wilmington, DeL, acorporation of Delaware No Drawing. Filed Apr. 15, 1964, Ser. No.360,121 7 Claims. (Cl. 106-273) The present invention relates to theproduction of asphaltic compositions, such as those used in pavingroads, which have a reduced stripping tendency.

Asphaltic mixtures composed of mineral aggregate and bituminousconstituents are widely used in the road construction industry. Thistype of paving composition, while economical and durable, has adisadvantage of being subject to deterioration by moisture. One type ofdeterioration results from the mineral aggregate having a greateraflinity for moisture than for asphalt. In many cases it is ditficult,if not impossible, to coat wet mineral aggregate satisfactorily withasphaltic compositons. Even when aggregate is already wet or coated withasphalt, water or water vapor slowly permeates the asphalt and loosensor strips the asphalt from the aggregate. Generally aggregatesconstitute from 80 to 85 percent of the bulk of a bituminous pavingmixture and from 90 to 95 percent of the weight of the mixture. Theeffect of water (susceptibility) is manifested at the interface betweenthe bituminous binder and the aggregate.

Aggregate used in road construction is hydrophilic, which means thatrock is preferentially wetted by water rather than by asphalt. At anybreak in an asphalt coating of a rock particle when water is present,the surfacetension forces work to disengage asphalt from aggregate andto contract asphalt films into islands lying on rather than adhering tothe rock surfaces.

The bituminous road building industry currently employs two methods forcoating road-type aggregates with asphalt, the hot mix method and theemulsion or cutback method. In the former, the aggregates are carefullydried by heat and then mixed with hot asphalt at temperatures of280-375" F. In the latter; the aggregates do not undergo a pretreatmentbut are simply cold mixed with an emulsion or solvent cutback of theasphalt.

Both methods have water as a common enemy. The hot mix method dependsupon pretreatment of the aggegate to remove water, while the emulsionmethod depends upon good mixing due to lower viscosity of the emulsion.In both methods, it is essential that the water be removed from theaggregate in order that the hydrophobic asphalt may properly coat theaggregate.

The coating and stripping problems briefly described above have led tothe incorporation of various chemicals with the asphalt mix to improvethe coating of the aggregates by the asphalt, and, once coated, toimprove adhesion of the asphalt to the aggregate. Typical of theseagents are the materials recited in US. Patents 2,706,688, 3,096,191,3,096,192, and 3,097,179.

In accord with the present invention an asphaltic mixture comprised ofasphalt and an anti-stripping additive selected from the group of aminesand amine salts consisting of: (1) a reaction product of an aminatingagent of ammonia or a primary or secondary amine containing from 1 to 6carbon atoms, for example, methyl amine,

3,3416% Patented Oct. 17, 1967 ethyl amine, diethyl amine, with an amineof the general formula:

R N/ H H x H A an. H 1'1 E f in which R is an alkyl or alkylene radicalcontaining between 12 and 20 carbon atoms, A is selected from the groupconsisting of H and CH and in which x and y are integers, one of whichmay be zero and x plus 1 equals from about 7 to about 27; (2) a reactionproduct of ammonia or a primary or secondary amine containing from 1 to6 carbon atoms, for example, methyl amine, ethyl amine, diethyl amine,with a hydroxy-containing material of the general formula:

it a wherein R contains from 12 to 20 carbon atoms and is selected fromthe group consisting of alkyl, alkylene, and alkaryl radicals, A isselected from the group consisting of H and CH and n is a number fromabout 3 to about 16; (3) salts of l) with a mineral acid or an organicacid selected from the group consisting of acetic, oleic, lauric,stearic, propionic, napthenic and resin acids, and; (4) salts of (2)with a mineral acid or an organic acid selected from the groupconsisting of acetic, oleic, lauric, stearic, propionic, naphthenic andresin acids.

The term asphal as used herein is meant to cover semi-solid or solidcementitious mixtures of natural or pyrogenous origin, or a combinationof both, in which bitumens are the sole or predominate constituent. Generally these mixtures are soluble or substantially soluble in carbonbisulfide. Naturally occurring or native asphalts and pyrogenousasphalts useful in the practice of the present invention includematerials such as albertite, elaterite, gilsonite, grahamite,wurtzilite, trinidad or hermudez lake asphalts, and those asphaltsobtained by refining petroleum by distillation, precipitation, cracking,solvent extraction, or similar operations, for example, distillationresidues, still bottoms, cracked residues, straightrun residues,asphaltic bitumens, and blown asphalt. Suitable asphalts may be in theform of solvent solutions or emulsions.

Descriptions of aminated polyoxyalkylene fatty amines, particularlythose of group 1) above, which are aptly suited to use in the presentinvention, along with descriptions of suitable methods of preparing suchamines, are given in detail in application No. 360,125, filed by John D.Zech, and in application No. 360,129, filed by R. A. Hales and F. A.Hughes, both of even date herewith. Generally, the arninated compoundsof group (2) above may be prepared by initially reacting ahydroxy-containing material, for example, nonyl phenol, with the desirednumber of moles of alkylene oxide by heating the reactants under aslight pressure to a temperature of around C. The alkylene oxideaddition reaction is advantageously carried out in the presence of analkaline catalyst such 3 as, sodium hydroxide or sodium methylate. Asuitable addition process is described in US. Patent 2,636,038, datedApr. 21, 1953 to John D. Brandner. The polyoxyalkylene product may thenbe aminated by heating with ammonia in the presence of a hydrogenationcatalyst, such as Raney nickel. Frequently, temperatures in the range offrom about 150 C. to about 275 C. are required. Suitable amines,particularly those of group (2) above, may be prepared by the methoddescribed in presently pending application No. 360,125, filed by John D.Zech, and in application No. 360,129, filed by R. A. Hales and F. A.Hughes, both of even date herewith. Suitable amines, particularly thoseof group (2) above, may be prepared by the method described in presentlypending application No. 360,125, filed by John D. Zech, and inapplication No. 360,129, filed by R. A. Hales and F. A. Hughes, both ofeven date herewith. The nomenclature utilized herein in referring to theamine materials useful in the present invention is to utilize the nameof the parent compound and precede that name by the number of aminogroups which have replaced hydroxyl groups. For example, an aminederived from 12 polyoxyethylene tridecyl alcohol is referred to as amino12 polyoxyethylene tridecyl alcohol. Examples of amines suited to use inthe present invention are: amino polyoxyethylene-nonylphenol, aminobis-(5 polyoxyethylene-nonylphenol), rnonoamino and di amino 20polyoxyethylene Armeen TD (Armeen TD is a product of Armour & Co.),amino bis-(6 polyoxyethylene-tridecylalcohol), and triamiuo 20polyoxyethylene sorbitol.

The term aggregate as used herein is meant to cover inert material, suchas sand gravel, shell, slag, or broken stone, or combinations thereof,which range in size from about 3 inch diameter pieces useful in macadarnpavements to sizes finer than a number USS screen useful in sheet andsand asphalt pavement mixtures. Filler materials, such as crusher dustand natural fines,,may also be included.

The asphaltic mixtures of the present invention in addition to beinguseful as a binder road construction material, are useful components inproducts such as foundry core binder mixtures, roof and pipe coatings,floor mastics, caulking compounds, and automobile undercoatingSufficient anti-stripping additive is generally used to give goodadhesiveness to the mixture. Generally upwards from about 0.1% by weightof the asphalt material is sufiicient to fulfill this requirement.Usually amounts of additive of over about 5.0% by weight of the asphaltmixture yield no obvious improvement. A suitable range of addi tivefound to be both efficient and economical for the present mixtures isfrom about 0.5 to about 1.5% by weight of the asphalt mixture.

The following examples shown in tabular form are illustrative of thepreparation of asphaltic mixtures compounded in accordance with thepresent invention. Each of the examples in the following table wereconducted in the same manner, e.g., in each case a 0.5 gram portion ofanti-stripping additive was mixed with a 100 gram portion of RC 3Cutback Asphalt (a product of Atlantic Refining Company) andthe mixtureheated at about 38 C. with stirring until uniform mixture was obtained.One gram of the asphalt plus additive mixture was then added to grams.of Ottawa sand. which was completely covered with 50 ml. of water andcontained in a 4 oz. bottle. This mixture was then hand shaken for 1minute followed by a 10 minute shaking on a laboratory shaker. Theinitial coating of the sand by the asphalt was noted as well as thepercentage of asphalt stripped from the sand during storage periods of 1and 2 hours at an elevated tern perature (100 C.) to acceleratestripping. The samples were then stored at 50 C. for a period of 64additional hours and the amount of stripping noted. The amount ofstripping was visually observed and qualitatively estimated bycomparison with a 100% coated sand sample. In Test 1 of the followingtable 0.5 gram of amino 5 polyoxyethylene nonylphenol was mixed with 100grams of RC 3 Cutback Asphalt and the mixture stirred and heated to,

38 C. until smoothpOne gram of the mixture was then added to a 4 oz.bottle containing 50 grams. of Ottawa sand covered by 50 ml. of water.The resultant mixture was hand shaken for 1 minute and machine shakenfor 10 minutes. The mixture was then heated to 100 C. and the percentageof stripping noted. After periods of 1 and. 2 hours no stripping wasnoted After an additional 64 hours at 50 C. the sample was againobserved and no stripping was evident. The organic acid salts of theamines were formed by mixing chemical equivalents of the amine and theacid together, forexample, in Test 2 equivalents of amino 5polyoxyethylene' nonylphenol and acetic acid were reacted by mixingtogether to form the acetate of the monoamine.

TABLE I Strippin (percent at Percent Initial g Anti-stripping additiveby Wt. Coating Nitrogen (percent) 100 0., 100 C., 50 0.,

1 Hour 2 Hours 64 Hours (1) Aminated 5 polyoxyethylene nonylphenoL. 2. 5100 0 O 0 (2) Acetate salt of (1).. 100 0 0 0 (3) Oleate salt of (1) 1000 0 0 (4) Aminated (5 polyoxyethylene nonylphenol). 0.9 100 25 50 50 (5)Acetate salt of (4) a 100 25 25 25 (6) Oleate Salt of (4) 100 25 25 25(7) Aminated 2O polyoxyethylene tallow amine (Armecn TD) 3. 4 100 O O 0(8) Acetate salt of (7)-. 100 0 0 0 (9) Oleate salt of (7) 100 0 0 0(10) Amlnated 6 polyoxyethylene tridecyl alcohol 2. 5 100 0 0 0 (11)Acetate salt of (10)-. 100 0 25 25 (12) Oleate salt of (10) 100 25 25 25(13) Aminated (6 polyoxyethylene tridecyl 0 alcohol) 1. 4 100 0 25 25(14) Acetate salt of (13) 100 25 25 25 (15) Oleate salt of (13)--- 100 00 0 (16) Aminated 12- polyoxyethylene tridecyl alcohol oleate l. 3 10025 50 50 (17) Aminated5polyoxyethylenetallowalcohol. 2.2 100 25 25 25(18) Aminated 13 polyoxyethylene tallow alcohol 1. 2 100 0 25 6 Table 2below shows the results of a series of tests a hydroxy-containingmaterial of the general formula carried out in a manner generallysimilar to the pro- H A cedure used in the tests shown in Table I. 80%by weight I I l of BM 1 asphalt (a product of Atlantic Refining Co.) OHin 20% by weight of naptha was utilized as the asphaltic 5 H Hcomponent. Various concentrations of anti-stripping adh i R contains f12 t 20 carbon atoms ditives were tested. Storage tests on variousconcentrand i selected from the group consisting of alkyl, tions wereconducted at 25 C. for 48 hours and at 50 alkylene and alkaryl radicals,A is selected from th for 48 hoursp In Test 19, ammo 5 P9 groupconsisting of H and CH and n is a number oxyethylene flonylphenol testedcoflcfinffatlofls 10 from about 3 to about 16, said reaction productbeing of and y Welght 1I11t1a1 Coatlng and prepared in the presence of ahydrogenation catalyst observed for the percentage of stripplng after 48hours and at a temperature from about 150 C, to about at 25 C. and 48hours at 50 C. 275 (3.,

TABLE II Initial Coating (percent) Percent Stripping at- Percent byAnti-Stripping Additive Wt. Ni- 48 Hours at 25 C. 48 Hours at 50 C.

trogen 0.5 1.0 1.5

(19) Aminaied 5 polyoxyethylcne nonylphenol 2. 5 100 (20) Acetate salt0t (19) 75 (21) Oleate salt of (19). 75 (22) Aminated 20 polyoxyethylenetallow amine (Armeen TD) 3.4 100 (23) Acetate salt of (22) 75 (24)Oleate salt of (22) 50 (25) Aminated 6 polyoxyethylene tridecyl alcohol2.5 100 (26) Acetate salt of (25) 75 (27) Aminated (6 polyoxyethylenetridecyl alcohol) 1. 4 0 (28) Aminated 12 polyoxyethylene tridecylalcohol 1.3 75

What is claimed is: (3) salts of (1) with an organic acid selectedfrom 1. An asphaltic mixture comprised of the group consisting ofacetic, oleic, lauric, stearic, asphalt, and propionic, naphthenic andresin acids, and; an anti-strlppmg additive selected from the group of(4) salts of (2) with an organic acid selected from the amines and aminederivatlves consisting of group consisting of acetic, oleic, lauric,stearic, 1) a reaction product of propionic, naphthenic and resin acids.

an aminating agent selected from the group con- 2. The mixture of claim1 with aggregate. sisting of ammonia, alkyl unsubstituted primary 3, Themixtur of lai 1 he i A i H, amines, and alkyl unsubstituted secondaryamlnes 4, Th mi tur of l i 1 h ei th antitripping containing from 1 to 6carbon atoms, with additive is a compound of the general formula amino 5polyoxyethylene-nonylphenol.

H A 5. The mixture of claim 1 wherein the anti-stripping l additive is II amino 6 polyoxyethylene tridecyl alcohol. H H x 6. The mixture ofclaim 1 wherein the anti-stripping H A additive iS amino bis-(6polyoxyethylene-tridecyl alcohol). I 7. The mixture of claim 1 whereinthe anti-stripping H H y additive is wherein R is selected from thegroup consisting of aminated 20 polyoxyethylene-tallow amine. alkyl andalkylene radicals containing between 12 and 20 carbon atoms, A isselected from the group consisting of H and CH and in which x and y areintegers one of which may be 0 and x plus y equals from about 7 to about27, said reaction product being prepared in the presence of ahydrogenation catalyst and at a temperature from about 150 C. to about275 C., (2) a reaction product of an aminating agent selected from thegroup consisting of ammonia, alkyl unsubstituted primary amines andalkyl unsubstituted secondary amines containing from 1 to 6 carbonatoms, with References Cited UNITED STATES PATENTS 2,508,429 5/1950Smith et al. 106-273 2,759,839 8/ 1956 Crews et al. 106-273 3,097,1797/1963 Ceintrey 106-277 XR ALEXANDER H. BR'ODMERKEL, Primary Examiner.DONALD J. ARNOLD, Examiner.

I. B. EVANS, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,347,690 October 17, 1967 Thomas J. Galvin et a1.

It is hereby certified that error appears in the above numbered patentrequiring correction and that the said Letters Patent should read ascorrected below.

Column 5, lines 42, 43, 65 and 66, for "alkyl unsubstituted", eachoccurrence, read unsubstituted alkyl Signed and sealed this 18th day ofMarch 1969.

(SEAL) Attest:

Edward M. Fletcher, Jr. EDWARD J. BRENNER Attesting Officer Commissionerof Patents

1. AN ASPHALTIC MIXTURE COMPRISED OF ASPHALT, AND AN ANTI-STRIPPINGADDITIVE SELECTED FROM THE GROUP OF AMINES AND AMINE DERIVATIVESCONSISTING OF (1) A REACTION PRODUCT OF AN AMINATING AGENT SELECTED FROMTHE GROUP CONSISTING OF AMMONIA, ALKYL UNSUBSTITUTED PRIMARY AMINES, ANDALKYL UNSUBSTITUTED SECONDARY AMINES CONTAINING FROM 1 TO 6 CARBONATOMS, WITH A COMPOUND OF THE GENERAL FORMULA